Rigid urethane foams from hydroxymethylated linseed oil and polyol esters

Rigid urethane foams were prepared from hydroxymethylated linseed oil and its esters of glycerol, trimethylolpropane and pentaerythritol. These polyols were made by selective hydroformylation with a rhodium-triphenylphosphine catalyst followed by catalytic hydrogenation with Raney nickel. Although the hydroxymethylated linseed monoglyceride by itself yielded a satisfactory foam, better foams were made from all hydroxymethylated linseed derivatives when blended with a low-molecular weight commercial polyol. Linseed-derived foams were compared with foams from equivalent formulations of hydroxymethylated monoolein and castor oil. Hydroxymethylated products yielded polyurethane foams meeting the requirements of commercial products with respect to density, compressive strength and dimensional stability. National Flaxseed Processors Association Fellow. N. Market. Nutr. Res. Div., ARS, USDA.     

Diels-Alder adducts from safflower oil fatty acids

Methyl esters of alkali-isomerized safflower oil fatty acids after elaidinization with sulfur were treated with styrene in the presence of hydroquinone, with or without solvents. A combination of column chromatography and gas liquid chromatography techniques was employed for the estimation of the methyl esters of unreacted fatty acids, Diels-Alder adduct and polymers in the reaction products. Maximum yield of the Diels-Alder adduct (26.6%) was obtained when the elaidinized methyl esters of the fatty acids were treated with 1.5 moles of styrene per mole of linoleic acid in safflower oil fatty acids at 200–210 C for 6 hr. The methyl ester of the adduct was isolated in about 90% purity from the reaction product by vacuum distillation followed by solvent fractionation. The butyl ester of the adduct and the epoxy derivative of the methyl ester adduct were prepared and characterized.     

Super acid catalyzed dimerization of fatty acids derived from safflower oil and dehydrated castor oil

Dimerization of fatty acids derived from dehydrated castor oil and safflower oil was carried out on the recently described sulphate-treated zirconia catalyst and trifluoromethane sulphonic acid (triflic acid) under autogeneous pressure in the temperature range of 160–240 C. Triflic acid was observed to be highly active; however, the product obtained was deeply colored. Zirconia exhibited high activity for the reaction. The important features of this catalyst were the high selectivity for dimer (low yields of trimer) and no significant coloration of the products. The zirconia catalyst shows promise for industrial use.     

Alkali catalyzed transesterification of safflower seed oil assisted by microwave irradiation

The safflower (Carthamus tinctorius L.) oil was extracted from the seeds of the safflower that grows in Diyarbakir, SE Anatolia of Turkey. Biodiesel has been prepared from safflower seed by transesterification of the crude oil under microwave irradiation, with methanol to oil molar ratio of 10:1, in the presence of 1.0% NaOH as catalyst. The conversion of C. tinctorius oil to methyl ester was over 98.4% at 6 min. The important fuel properties of safflower oil and its methyl ester (biodiesel) such as density, kinematic viscosity, flash point, iodine number, neutralization number, pour point, cloud point, cetane number are found out and compared to those of no. 2 petroleum diesel, ASTM and EN biodiesel standards. Compared with conventional heating methods, the process using microwaves irradiation proved to be a faster method for alcoholysis of triglycerides with methanol, leading to high yields of biodiesel.     

Polyurethane foams from hydroxymethylated fatty diethanolamides

Satisfactory rigid polyurethane foams were prepared from diethanolamides of hydroxymethylated oleate, linseed oil, safflower oil and their methyl esters. These foams were improved when the fatty polyols were blended with a commercial, low molecular weight polyol. National Flaxseed Processors Association Fellow. ARS, USDA.     

Some chemical processes utilizing oleic safflower oil

Oleic safflower seed (UC-1) produces an oil containing approximately 80% oleic acid and 12% linoleic acid. The oil is a source of high quality oleic acid, and fatty acids from the oil may be used without further separation in some applications where technical oleic acid is now used, since oleic safflower free fatty acids have a a higher oleic acid content than good commercial grades of oleic acid. A high purity oleic acid can be produced by urea fractionation. Ozonization of the oil followed by reductive cleavage yields pelargonaldehyde and nearly colorless aldehyde oils. Ozonization of a crude mixture of oleic safflower acids followed by oxidative cleavage provides high yields of azelaic acid and pelargonic acid. In contrast, ozonization of free fatty acids from polyunsaturated vegetable oils produces azelaic acid and mixtures of lower molecular weight carboxylic acids with smaller amounts of pelargonic acid. Furtherore, ozone consumption is lower and reaction time is shorter when oleic safflower acids are used in place of more highly unsaturated fatty acids.     

The role of safflower oil in edible oil applications

Safflower oil has been used as an edible oil in numerous countries for many years. In the US, commercial use of safflower oil as an edible product was noted in the 1950's and the use continues at progressively higher levels each year. One use of safflower oil in “dressing” type products is related to the natural cold resistance of the oil. Other applications include oil, margarine and some imitation dairy products. Additional development work has been done on other food products so that the scope of usage could be broadened if there should be increased demands for safflower oil. The susceptibility of safflower oil to oxidation has been minimized by improved processing and packaging. Further use of safflower oil appears to be dependent upon availability, pricing, good cold resistance and the role of polyunsaturates in the diet.     

Pilot-plant preparation of edible safflower oil

Summary Tests conducted on a pilot-plant scale with two lots of commercial, alkali-refined safflower oil demonstrate that no difficulty is experienced in producing a salad oil of good, initial quality with good flavor stability when stored at 60°C. in the dark. Although results indicate safflower oil is suitable for a salad oil, they should not be construed as indicating its stability as a cooking oil since tests of this type were not conducted. The addition of citric acid improved the oxidative stability of the oil, and citric acid plus propyl gallate gave even further improvement. No significant increase in flavor stability resulted from these additives. One of the divisions of the Agricultural Research Service, U. S. Department of Agriculture.     

Lipid-protein complexes from safflower expeller cake

Lipid-protein complexes were prepared from safflower prepress expeller cake, which contains about 18% oil and 17% protein, by grinding and extraction with aqueous alkali, then coprecipitation of oil and protein in the extract with acid. In the laboratory, using hammer mills or high-shear homogenizers, complexes were obtained containing up to 48% oil with 46% protein. In the pilot plant, the best extraction, using an attrition mill, yielded a complex contain-ing 44% oil and 47% protein. Phenolic glucosides, which contribute to the bitterness and cathartic activity in safflower meal, were removed during the process. Loaves of bread with 10% of the wheat flour replaced by safflower lipid-protein complexes had acceptable properties and contained 25-36% more protein than the controls.     

Oxidative stability of safflower oil

Oils from a number of varieties of safflower (Carthamus tinctorius L.) seeds (achene) were measured for oxidative stability by the gain in weight method. The induction periods of oils containing 75% to 80% linoleic acid ranged from 288 to 715 hr. Safflower oils containing 79% to 80% oleic acid and only 11% to 15% linoleic acid had induction periods ranging from 1274 to 2374 hr. No correlation between induction period and total tocopherol content was observed. However, there were indications that oils from pigmented seeds were less stable than oils from pigmentless seeds. Blending of an oil containing a high amount of linoleic acid with an oil containing a high amount of oleic acid gave a blend with an induction period intermediate between the two. However, the induction period was considerably less than the theoretical average calculated for the mixture. Arizona Agricultural Experiment Station Technical Paper No. 1389.     

Catalytic isomerization of safflower oil with rhodium complexes

Cationic rhodium (I) complexes of the type [(NBD)RhL₂]⁺ ClO₄ ⁻ (NBD, norbornadiene; L, triphenyl phosphine or diphenyl phosphino ethane) have been studied as catalysts for the isomerization of methyl linoleate and safflower oil. The catalysts gave very good yields of conjugated products with both oil and methyl linoleate. Isomerization could be carried out under very mild conditions (55–65 C, 1 atm N₂). Although the catalyst undergoes transformation in the course of the reaction, it maintains its catalytic activity. In fact, the catalysts isolated from the reaction with safflower oil were recycled with practically no loss of activity.     

High-oleic safflower oil. Stability and chemical modification

High-oleic acid safflower oil has been shown to have high-temperature oxidative stability comparable with that of hydrogenated vegetable oils. This stability, added to the ease of handling at low temperatures, should make the oil attractive as a commercial cooking oil. Epoxidation of the new safflower oil led to a product similar to epoxidized olive oil but lighter in color.     

Development and commercialization of GLA safflower oil

GLA safflower oil is a new commercial source of gamma‐linolenic acid (GLA), an important dietary omega‐6 fatty acid with properties similar and complementary to those of docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). In its native form, GLA safflower oil contains 60–70+% GLA. It is one of the first dietary supplements developed using modern biotechnology methods and is the first of a new generation of genetically modified (GM) plant oil ingredients developed solely for improvement of human health and nutrition.     

Effect of dietary safflower oil upon lipogenesis in neonatal lamb

The effect of dietary safflower oil upon lipogenesis has been investigated in neonatal lambs. Preliminary experiments with lambs suckled by their mothers showed that there was a 10-fold increase in the rate of incorporation of [¹⁴C] from acetate into fatty acids in adipose tissue slices during the first 10 days post partum. Barely detectable rates of [¹⁴C] acetate incorporation into fatty acids were found in liver slices from lambs during the same period. In lambs given cows' milk from birth until 11 days of age, there was also a 10-fold increase in the rate of lipogenesis in adipose tissue slices. Supplementing the diet of cows' milk with safflower oil (5 ml/lamb/day) resulted in significantly lower rates of lipogenesis in adipose tissue slices from 11 day old lambs. Administration of safflower oil had no effect upon the concentration of unesterified fatty acids, including linoleic acid, in the lamb adipose tissue slices. The data show that lipogenesis in ovine adipose tissue, like that in rodent liver and adipose tissue, is sensitive to dietary polyunsaturated fatty acids, and that, for the neonatal lamb, the effect of polyunsaturated fatty acids upon lipogenesis is not dependent upon an increase in the tissue concentration of polyunsaturated fatty acids.     

Synthesis of biodiesel fuel from safflower oil using various reaction parameters

Biodiesel fuel is gaining more and more importance because of the depletion and uncontrollable prices of fossil fuel resources. The use of vegetable oil and their derivatives as alternatives for diesel fuel is the best answer and as old as Diesel Engine. Chemically biodiesel fuel is the mono alkyl esters of fatty acids derived from renewable feed stocks like vegetable oils and animal fats. Safflower oil contains 75-80% of linoleic acid; the presence of this unsaturated fatty acid is useful in alleviating low temperature properties like pour point, cloud point and cold filter plugging point. In this paper we studied the effect of various parameters such as temperature, molar ratio (oil to alcohol), and concentration of catalyst on synthesis of biodiesel fuel from safflower oil. The better suitable conditions of 1:6 molar ratio (oil to alcohol), 60 degrees C temperature and catalyst concentration of 2% (by wt. of oil) were determined. The finally obtained biodiesel fuel was analyzed for fatty acid composition by GLC and some other properties such as flash point, specific gravity and acid value were also determined. From the results it was clear that the produced biodiesel fuel was with in the recommended standards of biodiesel fuel with 96.8% yield.     

American safflower seed oil

Summary The chemical and physical characteristics of a sample of hot pressed oil from saflower seed grown in Montana have been determined. This oil was found to contain 87.72 per cent of unsaturated acids, and 5.92 per cent of saturated acids. The composition of the oil has been determined with the following results, and, for comparison, results for sunflower seed and soy bean oils previously obtained, are also given. It will be observed that safflower oil contains a considerably larger proportion of linolic acid and less oleic acid than either of the other two oils, and this fact would account for its superior drying power.     

Composition of castor oil by optical activity

Summary The optical activity of castor oil and its derivatives has been studied. Pure methyl ricinoleate and methyl acetyl ricinoleate were prepared. The mixed methyl esters and acetylated methyl esters of castor oil were also prepared. By the determination of specific rotation of the pure and technical esters, the percentage of ricinoleate fraction can be deduced. This was calculated to be 93% and 90%, respectively. The esters of castor oil were calculated to contain 91.6% ricinoleate from the chemical hydroxyl value. This was about the average of the two values obtained optically and is believed close to the actual value. A number of castor oils were analyzed by both optical and chemical methods and found to be of nearly constant ricinoleic content. Dehydrated castor oil was found to have a comparative high specific rotation. This was believed due to its estolide content formed during dehydration.     

Cost of producing linoleic acid from safflower oil

Linoleic acid of 97% purity can be made from safflower oil by liquid-liquid extraction at a “cost to make” of about 21 cents a 1b. Calculations for the cost estimate were based on pilot-plant investigations. Fixed capital investment for a plant with an annual capacity of 20 million 1b has been estimated at approximately $1,800,000. Such a plant could be converted readily to the production of a variety of other fatty acids. A laboratory of the No. Utiliz. Res. & Dev. Div. ARS, U.S.D.A.     

Linoleic acid from safflower oil by liquid-liquid extraction

Summary Tests conducted on a pilot-plant scale have demonstrated that linoleic acid of about 95% purity may be produced from safflower fatty acids containing about 75% linoleic acid, by a liquid-liquid extraction process. Furfural was employed as the selective solvent, hexane as a secondary solvent, and the fractionation was made in a Podbielniak “double-pup” centrifugal extractor. Best results were obtained when the proc This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Microwave-assisted catalytic transfer hydrogenation of safflower oil

Catalytic transfer hydrogenation (CTH) of safflower oil was studied using aqueous ammonium formate as hydrogen donor and palladium on carbon as catalyst in a closed vessel under controlled microwave irradiation conditions. The method offered good selectivity in complete reduction of linoleic acid to monounsaturated acid with a slight increase in stearic acid compared to other reported catalytic transfer hydrogenation methods. Selectivity was achieved by using microwave-assisted CTH without employing an emulsifier or high ratios of water to oil.